JP6717830B2 - Aqueous dispersion of polymer particles containing pesticide and copolymerizable surfactant - Google Patents

Description

The present invention relates to an aqueous dispersion comprising a water-insoluble pesticide and polymer particles, the polymer particle comprising an alkoxylated copolymerizable surfactant in polymerized form. Further, the present invention relates to a method of preparing an aqueous dispersion by contacting water, a pesticide, and polymer particles. A further subject matter is a method for controlling the growth of phytopathogenic fungi and/or unwanted plants and/or attack of unwanted insects or mites, and/or a method for controlling the growth of plants, the aqueous dispersion comprising: Said pests, their environment or on the crop to be protected from each pest, on soil, and/or on undesired plants and/or crops and/or their environment; A seed containing a dispersion. The invention includes combinations of preferred features with other preferred features.

Agrochemical compositions containing polymer particles are known. WO 2010/086303 discloses seed dressing formulations comprising copolymers of various acrylate, acrylamide and alkyl acrylate monomers.

WO 2010/086303

The object of the present invention is to further improve pesticide formulations, for example with regard to their storage stability, their stability upon dilution, their resistance to rain, their biological activity, and to combat each pest. It was to reduce the amount of pesticide required.

The above objective was accomplished by an aqueous dispersion comprising a water insoluble pesticide and polymer particles, the polymer particles comprising, in polymerized form, an alkoxylated copolymerizable surfactant. ..

Aqueous dispersions generally relate to typical formulation types in the field of agricultural chemistry, emulsions, suspensions and suspoemulsions. In a preferred form, the aqueous dispersion is a suspending agent. In another preferred form, the aqueous dispersion is an emulsion. In yet another preferred form, the aqueous dispersion is a suspoemulsion.

In the case of suspensions, the aqueous dispersion is a water-insoluble pesticide, usually in the form of pesticide particles that are uniformly suspended in the continuous aqueous phase, and a suspension in the continuous aqueous phase. And turbid polymer particles.

In the case of emulsions, the aqueous dispersion is typically an oil-in-water emulsion. Emulsifiers usually comprise a non-water miscible solvent in the form of emulsified droplets that are uniformly emulsified in an aqueous continuous phase, the water-insoluble pest being present in the non-water-miscible solvent in dissolved form. To do. Emulsifiers usually further comprise polymer particles that are uniformly suspended in the continuous aqueous phase.

In the case of suspoemulsions, the aqueous dispersion usually comprises a non-water soluble pesticide in the form of pesticide particles and emulsified droplets that are uniformly emulsified in an aqueous continuous phase. Water-soluble pesticides are likewise present in dissolved form in non-water-miscible solvents. Suspoemulsions typically further comprise polymer particles that are uniformly suspended in the continuous aqueous phase.

However, other formulation types, such as capsule suspensions, dispersible concentrates, emulsifiable concentrates, flowable concentrates, water-in-oil emulsions, emulsifiable granules, emulsifiable gels, microemulsions and said formulation types. A mixture of, for example, ZC formulation (mixed formulation of capsule suspension and suspension concentrate), ZE formulation (mixed formulation of capsule suspension and Suspo emulsion), or ZW formulation (capsule suspension and oil-in-water emulsion) Mixed preparations of agents are also within the scope of the present invention.

The aqueous dispersion comprises a water insoluble pesticide. The term “water-insoluble” refers to pesticides having a solubility in water at 20° C. of not more than 10 g/l, preferably not more than 1 g/l, especially not more than 0.5 g/l.

Water-insoluble pesticides may be solid or liquid at room temperature and may be soluble in non-water miscible solvents.

Aqueous dispersions are usually water-insoluble pesticides in the form of suspended pesticide particles, or water-insoluble pesticides in the form of emulsion droplets containing the water-insoluble pesticide in dissolved form. Contains any of the biological agents.

The pesticide particles may be present at 20° C. in the form of solid crystalline or amorphous particles.

The pesticide particles or emulsion droplets usually have a particle size distribution (x50 value) of 0.1 to 10 μm, preferably 0.2 μm to 5 μm, particularly preferably 0.5 μm to 2.5 μm. The particle size distribution can be determined by laser light diffraction of an aqueous dispersion containing pesticide particles or emulsified droplets. The sample preparation (e.g. dilution to the measured concentration) depends on, among other things, the size and concentration of the pesticide particles and/or emulsified droplets in the sample and the equipment used (e.g. Malvern Mastersizer) in this measuring method. Will be decided. Preparative procedures must have been developed for the system and are known to those of ordinary skill in the art.

The term "pesticide" refers to at least one active substance selected from the group of fungicides, insecticides, nematicides, herbicides, safeners, biopesticides and/or growth regulators. Preferred pesticides are fungicides, insecticides, herbicides and growth regulators. Mixtures of two or more pesticides of the above class may also be used. Those skilled in the art are familiar with such pesticides and may be found, for example, in the Pesticide Manual, 16th Edition (2013), The British Crop Protection Council, London. Suitable insecticides are carbamate, organophosphate, organochlorine insecticide, phenylpyrazole, pyrethroid, neonicotinoid, spinosyn, avermectin, milbemycin, juvenile hormone analog, alkyl halide. , An organotin compound, a nereistoxin analogue, a benzoylurea, a diacylhydrazine, an insecticide selected from the METI acaricide class, and chloropicrin, pymetrozine, flonicamid, and clonicamide. Fentedine (clofentezine), hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorofenapyr, DNOC, buprofezin, ciloma cyromazine, amitraz, hydramethylnon, acequinocyl, fluacrypyrim, rotenone or their derivatives. Suitable fungicides include dinitroaniline, allylamine, anilinopyrimidine, antibiotics, aromatic hydrocarbons, benzenesulfonamide, benzimidazole, benzisothiazole, benzophenone, benzothiadiazole, benzo Triazine type, benzyl carbamate type, carbamate type, carboxamide type, carboxylic acid diamide type, chloronitrile type, cyanoacetamide oxime type, cyanoimidazole type, cyclopropane carboxamide type, dicarboximide type, dihydrodioxazine type, dinitrophenyl crotonate System, dithiocarbamate system, dithiolane system, ethylphosphonate system, ethylaminothiazolecarboxamide system, guanidine system, hydroxy-(2-amino)pyrimidine system, hydroxyanilide system, imidazole system, imidazolinone system, inorganic material system, isobenzofuranone System, methoxy acrylate system, methoxy carbamate system, morpholine system, N-phenyl carbamate system, oxazolidinedione system, oxyiminoacetate system, oxyiminoacetamide system, peptidylpyrimidine nucleoside system, phenylacetamide system, phenylamide system, phenylpyrrole system, Phenylurea type, phosphonate type, phosphorothiolate type, phthalamic acid type, phthalimide type, piperazine type, piperidine type, propionamide type, pyridazinone type, pyridine type, pyridinylmethylbenzamide type, pyrimidine amine type, pyrimidine type, Pyrimidinone hydrazone, pyrroloquinolinone, quinazolinone, quinoline, quinone, sulfamide, sulfamoyltriazole, thiazolecarboxamide, thiocarbamate, thiophanate, thiophene carboxamide, toluamide, triphenyltin compounds , Triazine-based and triazole-based classes of fungicides. Suitable herbicides include acetamide, amide, aryloxyphenoxypropionate, benzamide, benzofuran, benzoic acid, benzothiadiadinone, bipyridylium, carbamate, chloroacetamide, chlorocarboxylic acid, cyclohexane. Dione type, dinitroaniline type, dinitrophenol, diphenyl ether, glycine type, imidazolinone type, isoxazole type, isoxazolidinone type, nitrile type, N-phenylphthalimide type, oxadiazole type, oxazolidinedione type, oxyacetamide type, phenoxy type Carboxylic acid type, phenylcarbamate type, phenylpyrazole type, phenylpyrazoline type, phenylpyridazine type, phosphinic acid type, phosphoramidate type, phosphorodithioate type, phthalamate type, pyrazole type, pyridazinone type, pyridine type, pyridine type Carboxylic acid type, pyridinecarboxamide type, pyrimidinedione type, pyrimidinyl(thio)benzoate type, quinolinecarboxylic acid type, semicarbazone type, sulfonylaminocarbonyltriazolinone type, sulfonylurea type, tetrazolinone type, thiadiazole type, thiocarbamate type, triazine , Triazinone, triazole, triazolinone, triazolocarboxamide, triazolopyrimidine, triketone, uracil and urea herbicides.

Usually, the aqueous dispersion comprises in each case at least 5% by weight, preferably at least 10% by weight and particularly preferably at least 20% by weight, based on the total weight of the aqueous dispersion, of a water-insoluble pesticide. ..

The aqueous dispersion may further comprise a water-soluble pesticide in addition to the water-insoluble pesticide dissolved in the aqueous continuous phase of the aqueous dispersion. Preferably, the water-soluble pesticide has a solubility in water at 20° C. of more than 10 g/l, more preferably 20 g/l or more, most preferably 50 g/l or more.

The aqueous dispersion may contain from 0.1% to 50% by weight, preferably 0.5 to 40% by weight, most preferably 1 to 30% by weight of water-soluble pesticides.

Aqueous dispersions may include water immiscible solvents, which typically include water insoluble pesticides. The non-water miscible solvent may have a solubility in water at 20° C. of not more than 50 g/l, preferably not more than 20 g/l, especially not more than 5 g/l.

Suitable examples of non-water miscible solvents include:
Hydrocarbon solvents such as aliphatic, cyclic and aromatic hydrocarbons (e.g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, medium to high boiling mineral oil fractions (e.g. kerosene, diesel oil, coal tar). oil));
Vegetable oils such as corn oil, rapeseed oil;
Benzyl acetate;
Fatty acid esters, such as C ₁ -C ₁₀ -alkyl esters of C ₁₀ -C ₂₂ -fatty acids; or methyl or ethyl esters of vegetable oils, such as rapeseed oil methyl ester or corn oil methyl ester.

Mixtures of the solvents mentioned are also possible. Preferred solvents are aromatic hydrocarbons or benzyl acetate.

Suitable non-water miscible solvents are aromatic hydrocarbons. Aromatic hydrocarbons are compounds consisting of carbon and hydrogen and containing aromatic groups. Preferred are aromatic hydrocarbons or mixtures thereof having an initial boiling point of at least 160°C, preferably at least 180°C. Examples of aromatic hydrocarbons are mono- or polysubstituted with benzene, toluene, o-, m- or p-xylene, naphthalene, biphenyl, o- or m-terphenyl, C ₁ -C ₂₀ -alkyl. It is an aromatic hydrocarbon (eg ethylbenzene, dodecylbenzene, tetradecylbenzene, hexadecylbenzene, methylnaphthalene, diisopropylnaphthalene, hexylnaphthalene or decylnaphthalene). Other suitable water immiscible solvents are aromatic hydrocarbon mixtures having an initial boiling point of at least 160°C. Such compounds are commercially available, for example, from ExxonMobil or BP under the following trade names: Solvesso (registered trademark) 100, Solvesso (registered trademark) 150, Solvesso (registered trademark) 200, Solvesso (registered trademark). 150ND, Solvesso (registered trademark) 200ND, Aromatic (registered trademark) 150, Aromatic (registered trademark) 200, Hydrosol (registered trademark) A 200, Hydrosol (registered trademark) A 230/270, Caromax (registered trademark) 20, Caromax ( Registered trademark) 28, Aromat (registered trademark) K 150, Aromat (registered trademark) K 200, Shellsol (registered trademark) A 150, Shellsol (registered trademark) A 100, Fin (registered trademark) FAS-TX 150, Fin (registered trademark) Trademark) FAS-TX 200. Preferred aromatic hydrocarbons are aromatic hydrocarbon mixtures having an initial boiling point of at least 160°C, preferably at least 180°C. Mixtures of the abovementioned aromatic hydrocarbons are also possible.

Usually, the aqueous dispersion (preferably emulsion) is in each case 5 to 60% by weight, preferably 10 to 55% by weight, particularly preferably 20 to 45% by weight, based on the total weight of the aqueous dispersion. Contains a water miscible solvent.

The concentration of the water insoluble pesticide in the non-water miscible solvent can be at least 5% by weight of the non-water miscible solvent, preferably at least 10% by weight, most preferably at least 30% by weight.

When the aqueous dispersion is a suspending agent, said aqueous dispersion contains less than 10% by weight, preferably less than 1% by weight and most preferably less than 0.5% by weight of non-water-miscible solvents.

The aqueous dispersion may include a water soluble solvent. The water-soluble solvent may have a solubility in water at 20° C. of more than 50 g/l, preferably more than 100 g/l. Usually, the aqueous dispersions in each case comprise less than 10% by weight, preferably less than 3% by weight and particularly preferably less than 1% by weight, based on the total weight of the aqueous dispersion, of a water-soluble solvent. In one form, the aqueous dispersion is essentially free of water soluble solvents.

The aqueous dispersion contains water. The aqueous dispersion may comprise at least 5% by weight, preferably at least 10% by weight and particularly preferably at least 15% by weight, based on the total weight of the aqueous dispersion. The aqueous dispersion may comprise 20 to 85% by weight, preferably 30 to 75% by weight and particularly preferably 35 to 70% by weight of water, based on the total weight of the aqueous dispersion.

The aqueous dispersion further comprises polymer particles. The polymer particles include an alkoxylated copolymerizable surfactant in polymerized form.

The term "alkoxylated copolymerizable surfactant" generally relates to compounds having a reactive group, a backbone, at least one alkoxylate moiety and a hydrophobic anchor moiety.

The reactive group can participate in the polymerization reaction, thereby forming a covalent bond to other monomers in the polymer molecule.

Generally, the reactive groups are preferably selected from unsaturated aliphatic hydrocarbons linked to the backbone of the copolymerizable surfactant via a single bond, an ether, a ketone or an ester.

Examples of reactive groups are vinyl, allyl, 1-propenyl, 1-butenyl, 2-butenyl, isobutenyl and 3-butenyl.

Preferably, the reactive groups are selected from vinyl, allyl and 1-propenyl, preferably allyl and 1-propenyl, most preferably allyl.

The backbone of the copolymerizable surfactant may be covalently linked to the reactive group, the at least one alkoxylate and the hydrophobic anchor. Scaffold may be selected aliphatic and aromatic C ₂ -C ₁₀ hydrocarbons and from polyols containing 2 to 10 carbon atoms and 2 to 10 hydroxyl groups.

Preferably, the scaffold is selected aliphatic and aromatic C ₃ -C ₈ hydrocarbons, and from polyols containing 2 to 6 carbon atoms and 2 to 6 hydroxyl groups.

More preferably, the backbone is selected aliphatic and aromatic C ₃ -C ₆ hydrocarbons, and from polyols containing 2 to 4 carbon atoms and 2-4 hydroxyl groups.

Most preferably, backbone is selected from polyols containing aromatic C ₅ -C ₆ hydrocarbons, and three carbon atoms and three hydroxyl groups.

In one example, the scaffold is selected from pentadienyl, phenyl and glycerol, preferably phenyl and glycerol.

The copolymerizable surfactant is alkoxylated. The copolymerizable surfactant can have at least one alkoxylate moiety covalently linked to the backbone.

As used herein, the term "alkoxylate" generally refers to homopolymers and copolymers of alkylene oxide moieties containing 2, 3 or 4 carbon atoms (eg polyethylene oxide, polypropylene oxide or polybutylene oxide).

Preferably, the alkoxylate is polyethylene oxide or polypropylene oxide. More preferably, the alkoxylate is polyethylene oxide.

The repetition rate of the alkoxylates can be 1 to 1000, preferably 1 to 100, more preferably 3 to 50, most preferably 5 to 15. The term "repeat index" refers to the number of alkylene oxide repeat units.

Backbone normally be linked to the hydrophobic anchor is a C ₅ -C ₂₀ hydrocarbons. Preferably, the hydrophobic anchor, C ₅ -C ₁₅ hydrocarbon, more preferably a C ₉ -C ₁₅ hydrocarbon. Most preferably, the hydrophobic anchor is a C ₁₀ -C ₁₄ hydrocarbons.

The hydrophobic anchor may be aliphatic, aromatic, or may include a mixture of aromatic and aliphatic moieties. In one embodiment, the hydrophobic anchor is aliphatic. In another embodiment, the hydrophobic anchor comprises a mixture of aromatic and aliphatic moieties.

Examples of hydrophobic anchors are nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexyl-phenyl, heptyl-phenyl, octyl-phenyl, nonyl-phenyl with both branched and straight chain alkyl chains. , Decyl-phenyl and undecyl-phenyl moieties.

In one embodiment, the hydrophobic anchor, C ₁ -C ₁₄ - alkyl - phenyl, preferably C ₄ -C ₁₂ - alkyl - phenyl, more preferably C ₅ -C ₁₁ - alkyl - phenyl, most preferably C ₇ ~C ₁₁ -Alkyl-phenyl, especially C ₉ -alkyl-phenyl.

The alkoxylated copolymerizable surfactant may further comprise acidic moieties, such as carboxylic acid, sulfonic acid or phosphonic acid moieties, in protonated form or as salts of organic or inorganic cations.

For example, the copolymerizable surfactant is a reactive group selected from allyl and 1-propenyl, a skeleton selected from phenyl and glycerol, at least one polyethylene oxide moiety having a repeating index of 3 to 50, a hydrophobic anchor. C ₅ -C ₁₅ hydrocarbons, and sulfonic acid moieties.

In one embodiment, the copolymerizable surfactant, reactive group selected from 1-propenyl and allyl, backbone selected from aliphatic and aromatic C ₂ -C ₁₀ hydrocarbons, the repetition index of from 1 to 100 at least one polyethylene oxide moiety having, including C ₅ -C ₁₅ acid moiety by hydrocarbons, and optionally as a hydrophobic anchor.

In a preferred form, copolymerizable surfactant, reactive group selected from 1-propenyl and allyl, backbone selected from aliphatic and aromatic C ₃ -C ₆ hydrocarbon having a repetition index of 3-50 at least one polyethylene oxide moiety, aliphatic C ₉ -C ₁₅ hydrocarbon as the hydrophobic anchor, and a sulfonic acid moiety optionally.

In a more preferred form, the copolymerizable surfactant is a reactive group selected from 1-propenyl and allyl, a phenyl skeleton, at least one polyethylene oxide moiety having a repetition index of 3 to 50, an aliphatic as a hydrophobic anchor. Contains C ₉ -hydrocarbons, and sulfonic acid moieties.

In another embodiment, the copolymerizable surfactant is selected from reactive groups selected from allyl and vinyl ethers, allyl esters and vinyl esters, polyols containing 2 to 6 carbon atoms and 2 to 6 hydroxyl groups. skeleton that is, comprises at least one polyethylene oxide moiety, C ₅ -C ₂₀ acid moiety by hydrocarbons, and for the hydrophobic anchor having repeating index of 1 to 100.

In a preferred form, the copolymerizable surfactant is a reactive group selected from allyl ethers and allyl esters, a backbone selected from polyols containing 2 to 4 carbon atoms and 2 to 4 hydroxyl groups, 3 to at least one polyethylene oxide moiety having a repeating unit of 50, a hydrophobic anchor is selected from C ₅ -C ₂₀ hydrocarbons as hydrophobic anchor, and a sulfonic acid moiety.

In a more preferred form, the copolymerizable surfactant is a reactive group selected from allyl ethers and allyl esters, a glycerol backbone, at least one polyethylene oxide moiety having a repetition index of 5 to 15, an aliphatic C _{10 to} C ₁₄ It includes a hydrophobic anchor selected from a hydrocarbon and C _{7 to} C ₁₁ alkyl-phenyl, and a sulfonic acid moiety.

In one embodiment, the copolymerizable surfactant has the formula (I):

(In the formula,
R ¹ is a C _{5 to} C ₂₀ hydrocarbon group;
R ² and R ³ are each independently a hydrogen atom or methyl;
AO and AO' are each independently an alkylene oxide group having 2 to 4 carbon atoms;
X is H or SO ₃ ^- ;
The index x ranges from 0 to 12;
The index y is either 0 or 1;
The index z ranges from 1 to 10;
The index m ranges from 1 to 1000;
(The index n is in the range 0 to 1000)
Is a compound.

In one embodiment, the index n in formula (I) is 0. In another embodiment, the index y in formula (I) is 1. In yet another embodiment, the index x in formula (I) is 1.

The indices m and n in formula (I) may, independently of one another, be from 1 to 100, preferably from 3 to 50, more preferably from 5 to 15.

In another embodiment, both R ² and R ³ in formula (I) are hydrogen.

In one embodiment, AO and AO' in formula (I) are each independently an ethylene oxide group. In another embodiment, AO and AO' in formula (I) are each independently a propylene oxide group.

In a particularly preferred form, the copolymerizable surfactant has the formula (Ia):

(In the formula,
R ⁴ is C ₉ -C ₁₅ alkyl or C ₇ -C ₁₁ alkyl-phenyl,
X is H or SO ₃ ^- ,
(The index o is 3-50)
Is a compound.

Preferably, in Formula (Ia), residue R ⁴ is (more preferably C ₁₀ -C ₁₄ alkyl) C ₉ -C ₁₅ alkyl is, X is SO ₃ ^- and is, the index o is 5-15 ..

In one example, in the formula (Ia), R ⁴ is a C ₉ -C ₁₅ alkyl, X is SO ₃ ^- and is, o is in the range of 3 to 50. In another example, R ⁴ is C ₁₀ -C ₁₄ alkyl, X is SO ₃ ^- and is, the index o is 5-15.

In another embodiment, the copolymerizable surfactant has the formula (II):

(In the formula,
R ⁵ is C ₅ -C ₂₀ hydrocarbon group;
AO is an alkylene oxide group having 2 to 4 carbon atoms;
X is H or SO ₃ ^- ;
(The index n is in the range 1 to 1000)
Is a compound.

In one embodiment, AO in formula (II) is ethylene oxide. In another embodiment, AO in formula (II) is propylene oxide.

In one embodiment, the index n in formula (II) may be 1-100, preferably 3-50.

In one embodiment, R ⁵ is an aliphatic alkyl residue, preferably a C ₅ -C ₂₀ alkyl, more preferably C ₉ -C ₁₅ alkyl.

Alkoxylated copolymerizable surfactants of the type described above, such as alkoxylated copolymerizable surfactants according to formula (I), (Ia) or (II), are commercially available.

The alkoxylated copolymerizable surfactant is present in the polymer particles in polymerized form as monomer (I).

The polymer particles usually comprise 0.1 to 20% by weight, preferably 0.1 to 10% by weight and most preferably 0.5 to 5% by weight of monomer (I), based on the total amount of monomers.

In a preferred embodiment, the polymer particles comprise 0.1 to 10% by weight of the monomer (I), R ⁴ in formula (Ia) is C ₉ -C ₁₅ alkyl, X is SO ₃ ^- and is, index o Is in the range of 3 to 50.

In a more preferred embodiment, the polymer particles comprise 0.5 to 5 wt% of the monomer (I), R ⁴ in formula (Ia) is C ₁₀ -C ₁₄ alkyl, X is SO ₃ ^- and is, n Is in the range 5 to 15.

Polymer particles may further comprise a C ₂ -C ₁₂ alkyl (meth) acrylate as a monomer (II) in polymerized form. Preferably, C ₂ -C ₁₂ alkyl (meth) acrylates, C ₂ -C ₈ alkyl (meth) acrylate, more preferably a C ₂ -C ₆ alkyl (meth) acrylate.

As used herein, the abbreviation "(meth)acrylate" relates to methacrylate and/or acrylate.

Examples of suitable C ₂ -C ₁₂ alkyl (meth) acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl Methacrylate, heptyl methacrylate and octyl methacrylate. In a particularly preferred embodiment, C ₂ -C ₁₂ alkyl (meth) acrylate is butyl acrylate.

The polymer particles may comprise in polymerized form at least 10% by weight, preferably at least 20% by weight and most preferably at least 30% by weight of monomer (II), based on the total amount of monomers.

Furthermore, the polymer particles may comprise methyl (meth)acrylate as monomer (III) in polymerized form. Typically, the polymer particles contain at least 20% by weight, preferably at least 30% by weight and most preferably at least 40% by weight of monomer (III), based on the total amount of monomers.

The polymer particles may also contain (meth)acrylamide and (meth)acrylic acid as monomers (IV) in polymerized form. The weight ratio of (meth)acrylamide to (meth)acrylic acid can range from 10:1 to 1:10, preferably 5:1 to 1:5, most preferably 1:1 to 1:2.

The total amount of monomer (IV) in the polymer particles is typically in the range 0.1 to 10% by weight, preferably 0.5 to 5% by weight, most preferably 0.5 to 2% by weight, based on the total amount of monomers. ..

Usually, the polymer particles comprise 0.1 to 20% by weight of monomer (I) and at least 10% by weight of monomer (II) in polymerized form, based on the total amount of monomers.

In a preferred form of the invention, the polymer particles comprise 0.1 to 20% by weight of monomer (I), and at least 10% by weight of monomer (II), and at least 20% by weight of monomer (III), based on the total amount of monomers. In a polymerized form.

In a more preferred form of the invention, the polymer particles comprise 0.1 to 20% by weight of monomer (I) and at least 10% by weight of monomer (II), at least 20% by weight of monomer (III) and based on the total amount of monomers. It contains 0.1 to 10% by weight of monomer (IV) in polymerized form.

In the most preferred form of the invention, the polymer particles comprise 0.1 to 10% by weight of monomer (I), at least 20% by weight of monomer (II), at least 20% by weight of monomer (III) and It contains 0.5-5% by weight of monomer (IV) and the ratio of (meth)acrylamide to (meth)acrylic acid is 10:1 to 1:10.

In a particularly preferred form of the invention, the polymer particles comprise 0.5 to 5% by weight of monomer (I), at least 30% by weight of monomer (II), at least 40% by weight of monomer (III) and It contains 0.5-2% by weight of monomer (IV) and the ratio of (meth)acrylamide to (meth)acrylic acid is 5:1 to 1:5.

In particular, the polymer particles comprise 0.5-5% by weight of monomer (I), at least 30% by weight of monomer (II), at least 40% by weight of monomer (III) and 0.5-2% by weight, based on the total amount of monomers. It contains monomer (IV) and the ratio of (meth)acrylamide to (meth)acrylic acid is 1:1 to 1:2.

In one example, the polymer particles are
(I) a monomer in the form of an alkoxylated copolymerizable surfactant;
(II) C ₂ -C ₁₂ alkyl (meth) acrylate monomer;
(III) Methyl (meth)acrylate monomer; and
(IV) Contains (meth)acrylamide and (meth)acrylic acid monomers in polymerized form.

In another example, the polymer particles are
(I) Monomer in the form of an alkoxylated copolymerizable surfactant according to formula (I) or (II)
(II) C ₂ -C ₁₂ alkyl (meth) acrylate monomer;
(III) Methyl (meth)acrylate monomer; and
(IV) Contains (meth)acrylamide and (meth)acrylic acid monomers in polymerized form.

In another example, the polymer particles are
(I) a monomer in the form of an alkoxylated copolymerizable surfactant according to formula (I);
(II) C ₂ -C ₁₂ alkyl (meth) acrylate monomer;
(III) Methyl (meth)acrylate monomer; and
(IV) Contains (meth)acrylamide and (meth)acrylic acid monomers in polymerized form.

In yet another example, the polymer particles are
(I) a monomer in the form of an alkoxylated copolymerizable surfactant according to formula (Ia);
(II) C ₂ -C ₁₂ alkyl (meth) acrylate monomer;
(III) Methyl (meth)acrylate monomer; and
(IV) Contains (meth)acrylamide and (meth)acrylic acid monomers in polymerized form.

In yet another example, the polymer particles are
(I) Alkoxylated copolymerizability according to formula (Ia), wherein R ⁴ is C ₉ -C ₁₅ alkyl, X is SO ₃ ^- , and the index o is in the range 5-15. Monomers in the form of surfactants;
(II) C ₂ -C ₁₂ alkyl (meth) acrylate monomer;
(III) Methyl (meth)acrylate monomer; and
(IV) Contains (meth)acrylamide and (meth)acrylic acid monomers in polymerized form.

In yet another embodiment, the polymer particles are
(I) Alkoxylated copolymerizability according to formula (Ia), wherein R ⁴ is C ₁₀ -C ₁₄ alkyl, X is SO ₃ ^- , and the index o is in the range 5-15. Monomers in the form of surfactants;
(II) C ₂ -C ₈ alkyl (meth) acrylate monomer;
(III) Methyl (meth)acrylate monomer; and
(IV) Contains (meth)acrylamide and (meth)acrylic acid monomers in polymerized form.

In yet another embodiment, the polymer particles are
(I) Alkoxylated copolymerizability according to formula (Ia), wherein R ⁴ is C ₁₀ -C ₁₄ alkyl, X is SO ₃ ^- , and the index o is in the range 5-15. Monomers in the form of surfactants;
(II) butyl(meth)acrylate monomer; and
(III) Methyl (meth)acrylate monomer; and
(IV) Contains (meth)acrylamide and (meth)acrylic acid monomers in polymerized form.

In yet another embodiment, the polymer particles are
(I) Alkoxylated copolymerizability according to formula (Ia), wherein R ⁴ is C ₁₀ -C ₁₄ alkyl, X is SO ₃ ^- , and the index o is in the range 5-15. Monomers in the form of surfactants;
(II) Butyl acrylate monomer;
(III) Methyl methacrylate monomer; and
(IV) An acrylamide monomer and an acrylic acid monomer are contained in a polymerized form, and the weight ratio of acrylamide and acrylic acid is 5:1 to 1:5.

The polymer particles may comprise, in addition to the monomers (I) to (IV) listed above, at least one (eg 1 to 5) additional monomer (monomer (V)) in polymerized form.

Suitable additional monomers (V) include, for example, vinyl acetate, styrene, acrylonitrile, and mixtures thereof. Further examples are vinyltoluene; conjugated dienes (eg 1,3-butadiene and isoprene); α,β-monoethylenically unsaturated mono- and dicarboxylic acids or their anhydrides (eg itaconic acid, crotonic acid). , Dimethacrylic acid, allylacetic acid, vinylacetic acid, maleic acid, fumaric acid, mesaconic acid, methylenemalonic acid, citraconic acid, maleic anhydride, itaconic anhydride and methylmalonic anhydride); with maleic acid, fumaric acid or itaconic acid _{C 1 ~C 12, C 1 ~C} 8, or C ₁ -C ₄ esters of alkanols (e.g., dimethyl maleate and maleic acid n- butyl); N-tert-butylacrylamide, and N- methyl (meth) (Acrylamide); diacetone acrylamide; (meth)acrylonitrile; vinyl halides and vinylidene halides (eg vinyl chloride and vinylidene chloride); C ₁ -C ₁₈ vinyl esters of mono- or dicarboxylic acids (eg vinyl propionate, vinyl n- butyrate, vinyl laurate and vinyl stearate); 2 to 50 moles of ethylene oxide, propylene oxide, butylene oxide or alkoxylated C ₃ -C ₆ mono- mixtures thereof - or dicarboxylic acid (in particular acrylic acid, C ₁ -C ₄ hydroxyalkyl esters of methacrylic acid or maleic acid) or their derivatives, or with these acids, 2 to 50 moles of ethylene oxide, propylene oxide, C ₁ ~ which is alkoxylated with butylene oxide or mixtures thereof Esters of C ₁₈ alcohols (eg hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and methyl polyglycol acrylate); silane monomers; and monomers containing glycidyl groups (eg glycidyl methacrylate).

As another example of the monomer (V) which can be used, a linear 1-olefin, a branched 1-olefin or a cyclic olefin (for example, ethene, propene, butene, isobutene, pentene, cyclopentene, hexene and cyclohexene); A vinyl ether and an allylalkyl ether having 1 to 40 carbon atoms, wherein the alkyl group is as far as possible further substituents (e.g. hydroxyl group, amino group or dialkylamino group, or one or more alkoxylated groups). The above vinyl ether and allyl alkyl ether which may have (for example, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, vinyl cyclohexyl ether, vinyl 4-hydroxybutyl ether, decyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, 2- (Diethylamino)ethyl vinyl ether, 2-(di-n-butylamino)ethyl vinyl ether, methyldiglycol vinyl ether, and the corresponding allyl ether); sulfo-functional monomers (eg, allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonate, Allyloxybenzenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and their corresponding alkali metal or ammonium salts, sulfopropyl acrylate and sulfopropyl methacrylate); vinylphosphonic acid, dimethylvinylphosphonate, and other phosphorus monomers Alkylaminoalkyl(meth)acrylates or alkylaminoalkyl(meth)acrylamides or their quaternized products (eg, 2-(N,N-dimethylamino)ethyl(meth)acrylate, 3-(N,N- Dimethylamino)propyl(meth)acrylate, 2-(N,N,N-trimethylammonium)ethyl(meth)acrylate chloride, 2-dimethylaminoethyl(meth)acrylamide, 3-dimethylaminopropyl(meth)acrylamide, and 3 -Trimethylammonium propyl (meth)acrylamide chloride); C _{1 to} C ₃₀ monocarboxylic acid allyl ester; N-vinyl compounds (eg, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylpyrrolidone, N -Vinylimidazole, 1-vinyl-2-methylimidazole, 1-vinyl-2-methylimid Dazoline, N-vinylcaprolactam, vinylcarbazole, 2-vinylpyridine, and 4-vinylpyridine).

As the monomer (V) used, a crosslinking monomer such as divinylbenzene; 1,4-butanediol diacrylate; a monomer containing a 1,3-diketo group (eg, acetoacetoxyethyl (meth)acrylate or diacetone acrylamide); And monomers containing urea groups (eg, ureidoethyl (meth)acrylate, acrylamidoglycolic acid, and methacrylamide glycolate methyl ether); and silane crosslinkers (eg, 3-methacryloxypropyltrimethoxysilane and 3-mercaptopropyltriether). Methoxysilane). Further examples of crosslinkers are N-alkylolamides of α,β-monoethylenically unsaturated carboxylic acids having 3 to 10 carbon atoms and their esters with alcohols having 1 to 4 carbon atoms. (Eg, N-methylol acrylamide and N-methylol methacrylamide); glyoxal-based crosslinkers; monomers containing two vinyl groups; monomers containing two vinylidene groups; and monomers containing two alkenyl groups. To be Exemplary crosslinking monomers include diesters or triesters of dihydric and trihydric alcohols with α,β-monoethylenically unsaturated monocarboxylic acids (e.g., di(meth)acrylate, tri(meth)acrylate). Of these, acrylic acid and methacrylic acid can now be used. Examples of such monomers containing two unconjugated ethylenically unsaturated double bonds are alkylene glycol diacrylates and dimethacrylates, such as ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1, 4-butylene glycol diacrylate and propylene glycol diacrylate, vinyl methacrylate, vinyl acrylate, allyl methacrylate, allyl acrylate, diallyl maleate, diallyl fumarate and methylenebisacrylamide. The crosslinking monomer, when used in the copolymer, may be present in an amount of 0.2% to 5% by weight, based on the weight of total monomers. Generally, the polymer does not include crosslinking monomers.

The polymer particles described herein use free radical emulsion polymerization to polymerize monomers (e.g., monomer (I), and optionally monomers (II), (III), (IV) and (V)). Can be prepared by. The emulsion polymerization temperature is generally 30°C to 95°C or 75°C to 90°C. Examples of the polymerization medium include water alone or a mixture of water and a water-miscible liquid (eg, methanol). In some embodiments, water is used alone. Emulsion polymerization can be performed either as a batch process, a semi-batch process, or a continuous process. Typically, a semi-batch process is used. In some embodiments, a portion of the monomers is heated to the polymerization temperature to partially polymerize and then the remaining portion of the polymerization batch is fed continuously, stepwise or by superimposing concentration gradients to the polymerization zone. can do. Alternatively, other heterophasic polymerization methods such as miniemulsion polymerization can be used. Further examples of the polymerization method include, for example, the polymerization method described in Antonietti et al., Macromol. Chem. Phys., 204:207-219 (2003), which is herein incorporated by reference. Incorporated into.

Free radical emulsion polymerization can be carried out in the presence of a free radical polymerization initiator. Free radical polymerization initiators that can be used in the above steps are all free radical polymerization initiators that can initiate free radical aqueous emulsion polymerization, such as alkali metal peroxydisulfate and H ₂ O ₂ , Alternatively, an azo compound may be used. Complex systems containing at least one organic reducing agent and at least one peroxide and/or hydroperoxide (e.g. tert-butyl hydroperoxide and hydroxymethanesulfinic acid, or hydrogen peroxide and ascorbic acid) can also be used. .. A small amount of a metal compound that is soluble in the polymerization medium and whose metal component can exist in two or more oxidation states (for example, ascorbic acid/iron(II) sulfate/hydrogen peroxide, ascorbic acid is sodium hydroxymethanesulfinate). It may be replaced by a metal salt, sodium sulfite, sodium bisulfite or sodium metal bisulfite, hydrogen peroxide being replaced by tert-butyl hydroperoxide or an alkali metal peroxydisulfate and/or ammonium peroxydisulfate. Can also be used. Carbohydrate-derived compounds can also be used as reducing components in complex systems. Generally, the amount of free radical initiator system used can be 0.1 to 2%, based on the total amount of monomers polymerized. In some embodiments, the initiator is ammonium and/or alkali metal peroxydisulfate (eg, sodium persulfate), either alone or as a component of a complex system. The method of adding the free radical initiator system to the polymerization reactor during the free radical aqueous emulsion polymerization is not critical. All may be initially introduced into the polymerization reactor or may be added continuously or in stages as they are consumed during the free radical aqueous emulsion polymerization. In particular, this depends on both the chemistry of the initiator system and the polymerization temperature, in a manner known to those of ordinary skill in the art. In some embodiments, a portion is introduced first and the remaining portion is added to the polymerization zone as it is consumed. It is also possible to carry out free radical aqueous emulsion polymerization under ultra high pressure or under reduced pressure.

One or more polymeric surfactants can be included to improve certain properties of the dispersion, including particle stability. For example, sodium laureth sulfate surfactant, sodium hexametaphosphate surfactant, tetrasodium pyrophosphate surfactant, tetrapotassium pyrophosphate surfactant, and alkylbenzene sulfonic acid surfactant or sulfonate surfactant can be used. right. Examples of commercially available surfactants are CALFOAM ES-303 (Pilot Chemical Company; Cincinnati, Ohio); DOWFAX 2A1 (alkyldiphenyl oxide disulfonate surfactant available from Dow Chemical Company, Midland, MI); and ALCOSPERSE. 149 (sodium polyacrylate surfactant available from Akzo Nobel Surface Chemistry (Chicago, Ill.)). Generally, the amount of polymerizing surfactant used can be 0.01 to 5%, based on the total amount of monomers polymerized.

Polymerizing surfactants generally cannot react during the polymerization reaction and therefore do not form any covalent bonds to the polymer particles.

Further, in order to adjust the film-forming properties of the polymer, the polymer particles may contain what is known as a film-forming solidifying agent (plasticizer), examples of which include ethylene glycol, propylene glycol, butylene glycol, and Alkyl ethers and alkyl ether esters of xylene glycol, glycol and polyglycol (for example, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, hexylene glycol diacetate, propylene glycol monoethyl ether, monophenyl ether, monobutyl ether) And monopropyl ether, dipropylene glycol monomethyl ether, and mono-n-butyl ether, tripropylene glycol mono-n-butyl ether), and acetic acid ester of said monoalkyl ether (for example, butoxybutyl acetate), and also aliphatic mono-and Alkyl esters of dicarboxylic acids (eg Texanol® from Eastman) or technical grade mixtures of dibutyl esters of succinic acid, glutaric acid and adipic acid. Film forming aids are conventionally used in amounts of 0.1 to 20 weight percent based on the polymer. In one form the polymer particles comprise less than 5% by weight, preferably less than 2% by weight and especially less than 0.3% by weight of plasticizer. Preferably, the polymer particles are free of plasticizer.

Small amounts (eg 0.01 to 2% by weight, based on total monomer weight) of molecular weight regulators, such as mercaptans, can optionally be used. Such materials are preferably added to the polymerization zone as a mixture with the monomers to be polymerized and are considered as part of the total amount of unsaturated monomers used in the copolymer.

The average molecular weight of the polymer is usually 10,000 to 5,000,000 Da, preferably 100,000 to 1,000,000 Da, in particular 300,000 to 800,000 Da.

The glass transition temperature (T _g ) of the polymer particles is usually −10 to 30° C., more preferably 0 to +20° C., especially 5 to 15° C. The glass transition temperature of a polymer can be determined by differential scanning calorimetry (DSC), for example, according to the following procedure: Effect of water/solvent on copolymer T _g after drying all samples for 1 hour at 110°C. Can be removed. The sample size for DSC can be about 10-15 mg. The measurement is usually performed from -100°C to 100°C at 20°C/min under N ₂ atmosphere. The T _g can be determined by the midpoint of the transition region.

The glass transition temperature typically depends on the monomer composition and the average molecular weight of the polymer particles. Those skilled in the art can manipulate the T _g by varying the monomer concentration and the average molecular weight of the polymer. Generally, increasing the concentration of alkoxylated copolymerizable surfactant results in a decrease in T _g , but relatively high average molecular weight can increase T _g .

The particle size of the polymer particles is usually 1000 μm or less, preferably 500 μm or less, preferably 250 μm or less, and particularly 150 μm or less. The particle size of the polymer particles is usually 10 to 1000 nm, preferably 30 to 300 nm, especially 50 to 150 nm. The particle size is usually the average particle size (z-average) of the polymer particles. Particle size can be determined by dynamic light scattering (photon correlation spectroscopy) on a 0.01 weight percent dispersion in water at 23°C.

Polymer particles are usually insoluble in water at 20°C.

The polymer particles can be used or prepared in the form of an aqueous dispersion of polymer particles. The solids content of the dispersion may be 20-80% by weight.

The polymer particles are typically essentially free of pesticides. The term "essentially free of pesticides" refers to a concentration of less than 5% by weight, based on the total weight of the polymer particles. In a preferred embodiment, the polymer particles comprise less than 2% by weight and in a particularly preferred embodiment less than 0.1% by weight of pesticides, based on the total weight of the polymer particles.

The concentration of the pesticide in the polymer particles can be determined by separating the polymer particles from the aqueous dispersion by standard techniques known to those skilled in the art (e.g. centrifugation) and separating the isolated polymer particles with an organic solvent (e.g. It can be measured by extracting the pesticide with (methanol, dichloromethane, acetone or acetonitrile). Quantitation of pesticides in the extract can be achieved by HPLC analysis. The concentration can be calculated from the amount of polymer particles separated and the pesticide extracted.

In general, the aqueous dispersions in each case comprise from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight and particularly preferably from 0.5 to 7% by weight, based on the total weight of the aqueous dispersion, of the polymer particles.

In one form, the aqueous dispersion is in each case at least 5% by weight, based on the total weight of the aqueous dispersion, of a water-insoluble pesticide (e.g. solubility in water of 10 g/l or less), 0.1-20 wt. % Polymer particles, wherein the polymer particles comprise 0.1-10 wt% monomer (I), at least 20 wt% monomer (II), at least 20 wt% monomer (III), 0.1-10 wt% monomer (I). IV) in polymerized form, the weight ratio of acrylamide to acrylic acid is 10:1 to 1:10.

In another form, the aqueous dispersion is in each case at least 10% by weight, based on the total weight of the aqueous dispersion, of a water-insoluble pesticide (solubility in water of 1 g/l or less), 0.5-10 wt. % Polymer particles, wherein the polymer particles comprise 0.5-5 wt% monomer (I), at least 30 wt% monomer (II), at least 40 wt% monomer (III), 0.5-2 wt% monomer (I). IV) in polymerized form, and the weight ratio of acrylamide to acrylic acid is 5:1 to 1:5.

In another form, the aqueous dispersion is in each case at least 20% by weight, based on the total weight of the aqueous dispersion, of a water-insoluble pesticide (solubility in water of 1 g/l or less), 0.5-7% by weight. % Polymer particles, wherein the polymer particles comprise 0.5-5 wt% monomer (I), at least 30 wt% monomer (II), at least 40 wt% monomer (III), 0.5-2 wt% monomer (I). IV) in polymerized form and the weight ratio of acrylamide to acrylic acid is 1:1 to 1:2.

The aqueous dispersion may contain auxiliaries for pesticide formulations. Examples of suitable auxiliaries are solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, auxiliaries, solubilizers, penetration enhancers, protective colloids, adhesives, thickeners, humectants, Repellents, attractants, feeding stimulants, compatibilizers, bactericides, antifreeze agents, defoamers, colorants, tackifiers and binders.

Suitable solid carriers or fillers are mineral earths such as silicates, silica gel, talc, kaolin, limestone, lime, chalk, clay, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders such as cellulose. , Starch; fertilizers such as ammonium sulphate, ammonium phosphate, ammonium nitrate, urea; products of plant origin such as cereal flour, bark flour, wood flour, nut shell flour, and mixtures thereof.

Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifiers, dispersants, solubilizers, wetting agents, penetration enhancers, protective colloids or auxiliaries. Examples of surfactants are listed in McCutcheon's, Vol. 1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (international edition or North American edition).

Suitable anionic surfactants are sulphonates, sulphates, phosphates, alkali, alkaline earth or ammonium salts of carboxylates and mixtures thereof. Examples of sulfonates are alkyl aryl sulfonates, diphenyl sulfonates, alpha-olefin sulfonates, lignin sulfonates, fatty acid and oil sulfonates, ethoxylated alkylphenol sulfonates, alkoxylated arylphenol sulfonates, condensed naphthalene sulfonates, dodecylbenzene and tridecylbenzene. Sulfonate, naphthalene and alkylnaphthalene sulfonate, sulfosuccinate or sulfosuccinamate. Examples of sulphates are sulphates of fatty acids and oils, sulphates of ethoxylated alkylphenols, sulphates of alcohols, sulphates of ethoxylated alcohols or sulphates of fatty acid esters. An example of a phosphate is a phosphate ester. Examples of carboxylates are alkyl carboxylates and carboxylated alcohols or alkylphenol ethoxylates.

The aqueous dispersion preferably comprises an anionic surfactant. A preferred anionic surfactant is a sulfonate, more preferably a fused naphthalene sulfonate. The aqueous dispersion may contain from 0.1 to 12% by weight, preferably 0.5 to 7% by weight and especially 1 to 4% by weight of anionic surfactants (eg sulphonates).

Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which are alkoxylated in 1 to 50 equivalents. Ethylene oxide and/or propylene oxide (preferably ethylene oxide) can be used for the alkoxylation. Examples of N-substituted fatty acid amides are fatty acid glucamide or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitan, ethoxylated sorbitan, sucrose and glucose esters or alkyl polyglucosides. Examples of polymeric surfactants are vinylpyrrolidone, vinyl alcohol or vinyl acetate home polymers or copolymers.

Suitable cationic surfactants are quaternary surfactants (eg quaternary ammonium compounds having one or two hydrophobic groups), or salts of long-chain primary amines. Suitable amphoteric surfactants are alkyl betaines and imidazolines. Suitable block polymers are A-B or A-B-A type block polymers containing blocks of polyethylene oxide and polypropylene oxide, or A-B-C type block polymers containing alkanols, polyethylene oxide and polypropylene oxide.

Suitable auxiliaries are compounds whose pesticidal activity is negligible or has no pesticidal activity itself and which enhances the biological performance of the pesticide against its target. Examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are given in Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, Chapter 5.

Suitable thickeners are polysaccharides (eg xanthan gum, carboxymethylcellulose), inorganic clays (organic modified or unmodified clay), polycarboxylates, and silicates.

Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.

Suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerin.

Suitable defoamers are salts of silicones, long chain alcohols and fatty acids.

Suitable colorants (eg red, blue, green) are low water soluble pigments and water soluble dyes. Examples are inorganic colorants (eg iron oxide, titanium oxide, hexacyanoferrate) and organic colorants (eg alizarin colorants, azo colorants and phthalocyanine colorants).

Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyacrylates, biological or synthetic waxes, and cellulose ethers.

The aqueous dispersion can be used for the purpose of treating plant propagation material, especially seeds. The composition gives an active substance concentration of 0.01 to 60% by weight, preferably 0.1 to 40% by weight, in a ready-to-use preparation after a 2 to 10-fold dilution. Application can be carried out before sowing or during sowing. Examples of the method for applying or treating the aqueous dispersion onto plant propagation material (particularly seed) include, for example, dressing method of the propagation material (dressing), coating method (coating), pelleting method (pelleting), and dusting method (dusting). ), a soaking method, and an in-furrow method. Preferably, the aqueous dispersion is applied to the plant propagation material in such a way that germination is not induced, for example by seed dressing, seed pelleting, seed coating and seed dusting.

When used in plant protection, the amount of active substance applied is, depending on the type of effect desired, 0.001 to 2 kg per hectare (ha), preferably 0.005 to 2 kg per hectare (ha), more preferably It is 0.05 to 0.9 kg per hectare (ha), especially 0.1 to 0.75 kg per hectare (ha). For example, in the treatment of plant propagation material (e.g. seeds) by means of seed dusting, coating or irrigation (drenching), 0.1 to 1000 g of active substance per 100 kg of plant propagation material (preferably seed). An amount of, preferably 1 to 1000 g, more preferably 1 to 100 g, most preferably 5 to 100 g is generally required. When used in the protection of materials or stored products, the amount of active substance applied depends on the area of application and the kind of effect desired. The amount conventionally applied in the protection of materials is 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active substance per cubic meter of the material to be treated.

Various types of oils, humectants, auxiliaries, fertilizers or micronutrients and other pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) in aqueous dispersions. , As a premix or, if appropriate, just before use (tank mix). These agents can be admixed with the aqueous dispersions according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

The user usually applies the aqueous dispersion or a tank mix prepared from the aqueous dispersion from a predosage device, a backpack sprayer, a spray tank, a spray airplane or an irrigation system. Usually, the aqueous dispersions are brought to the desired application concentration with water, buffers and/or further auxiliaries, thus obtaining ready-to-use spray liquors or aqueous dispersions according to the invention. Usually, 20-2000 liters, preferably 50-400 liters of ready-to-use spray liquor are applied per hectare of agriculturally useful area.

The invention further relates to a process for preparing an aqueous dispersion by contacting water, a water-insoluble pesticide, and polymer particles, and optionally auxiliary agents. Contact is in a known manner, for example as described in Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005. Can be achieved. Contacting is usually accomplished by mixing (eg in a high shear mixer) at ambient temperature (eg 10-40° C.).

The present invention further provides a method for controlling phytopathogenic fungi and/or unwanted plant growth and/or unwanted insect or mite attack, and/or a method for controlling plant growth, which comprises an aqueous dispersion. , Said pests, their environment or crops to be protected from each pest, on soil, and/or on undesired plants and/or crops and/or their environment.

Examples of suitable crops are cereals (for example wheat, rye, barley, triticale, oats or rice); beets (for example sugar beet or forage beet); pome fruit, drupe and soft fruits (for example apple, pear, Plums, peaches, almonds, cherries, strawberries, raspberries, currants or gooseberries); legumes (eg, legumes, lentils, peas, alfalfa or soybeans); oil crops (eg, oilseed rape, mustard, olives, sunflowers, coconuts, Cocoa bean, castor oil beans, oil palm, peanut or soybean); Cucurbitaceae (eg pumpkin/pumpkin, cucumber or melon); Fiber crops (eg cotton, flax, hemp or jute); Citrus (eg orange, lemon, grapefruit or Mandarin); Vegetables (for example spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, pumpkins/pumpkins or capsicum); Bay plants (for example avocado, cinnamon or camphor); Energy crops and industrial crops ( For example, corn, soybean, wheat, rapeseed, sugar cane or oil palm); corn; tobacco; nuts; coffee: tea; bananas; grapes (dessert and brewing grapes); hops; grass (eg lawn); (Stevia rebaudania); natural rubber plants and forest plants (eg flowers, shrubs, deciduous and coniferous trees); breeding materials (eg seeds) and harvested produce of these plants.

The term "crop" also includes plants that have been modified by breeding, mutagenesis or recombinant methods, including commercially available or underdeveloped biotech produce. A “genetically modified plant” is a plant whose genetic material has been modified by crossing, mutagenesis or natural recombination (ie recombination of genetic material) in a manner that does not occur under natural conditions. Here, one or more genes are generally incorporated into the genetic material of the plant to improve the properties of the plant. Such recombinant modifications also include, for example, post-translational modification of proteins, oligopeptides or polypeptides with glycosylated or linked polymers (eg, prenylated, acetylated or farnesylated residues or PEG residues).

The invention further relates to seed comprising the aqueous dispersion.

The advantage of the aqueous dispersions according to the invention is their high storage stability, even at varying temperatures, high or low temperatures. In particular, no phase separation or aggregation is observed during storage. Furthermore, the aqueous dispersions show a high stability when diluted, which increases their applicability for agrochemical purposes. Other advantages include high rain resistance of the aqueous dispersion on crops, increased biological efficacy of the aqueous dispersion, and consequent increase in the amount of pesticide needed to control each pest. Reduction.

The following examples illustrate the invention without imposing any limitation.

Polymer particle A: Particle size (x50) 100 nm; T _g 10°C; Monomer composition: 53 wt% butyl acrylate, 44 wt% methyl methacrylate, 0.9 wt% acrylic acid, 0.5 wt% acrylamide and 1.25 wt% monomer (Ia)( Where R ⁴ is C ₁₀ -C ₁₄ alkyl, X is SO ₃ Na, and the index o is 10-40).
Polymer particle B: Particle size (x50) 100 nm; T _g 10°C; Monomer composition: 53 wt% butyl acrylate, 43 wt% methyl methacrylate, 1.8 wt% acrylic acid, 1.0 wt% acrylamide and 1.25 wt% monomer (Ia) Where R ⁴ is C ₁₀ -C ₁₄ alkyl, X is SO ₃ Na, and the index o is 10-40.
Comparative particles C: Particle size (x50) 150 nm; T _g 22° C.; Monomer composition: 48 wt% butyl acrylate, 49 wt% methyl methacrylate, 1.8 wt% acrylic acid, 1.0% acrylamide.
Solvent A: Aromatic hydrocarbon, initial boiling point 231°C, flash point 105°C
Surfactant A: C ₁₈ fatty alcohol ethoxylates, 2-4 EO units per molecule.
Surfactant B: ethoxylated castor oil, HLB value 14-15.
Surfactant C: C ₄ alcohol ethoxylate, HLB value 16-18.
Surfactant D: ethoxylated and propoxylated C ₁₂ -C ₁₈ alcohol alkoxylates.
Surfactant E: block copolymer of ethylene oxide and propylene oxide, HLB 12-18, average molecular weight 6500.
Thickener: Xanthan gum.
Wetting agent: sodium salt of a naphthalene sulfonate condensate.
Defoamer: Silicone defoamer.
Biocide: An aqueous mixture of 2-methyl-4-isothiazolin-3-one and 1,2-benzisothiazolin-3-one.

Example 1
Emulsified alpha-cypermethrin, chlorfenapyr and pyraclostrobin aqueous emulsions (AE1, AE2 and AE3) were prepared by dissolving each pesticide in solvent A. did. An aqueous phase containing other auxiliaries (surfactants A, B and/or C, polymer particles A, defoamers and propylene glycol) is mixed with the oil phase and the oil droplet size is less than 3 μm in a high shear mixer. It was homogenized at 7,000 rpm until. Finally, the thickener and biocide were added under stirring. The final concentrations of the ingredients are shown in Table 1.

Table 1: AE1 to AE3, concentrations are shown in [% by weight].

Example 2:
The storage stability of each of AE1 and AE2 is as follows: one sample at 54°C for 2 weeks, another sample at a daily circulation temperature of -10°C to +10°C for 2 weeks, and another sample at -10°C. Each was tested for 2 weeks.

The storage stability of AE3 was 1 sample for 2 weeks at 54 °C, another sample for 2 weeks at a daily circulation temperature of -10 °C to +30 °C, and another sample for 2 weeks at 21 °C. Another sample was tested at -10°C for 2 weeks.

Emulsion stability was determined by visual observation of the sample. No significant phase separation occurred for all storage temperatures of samples AE1 to AE3.

Oil drop size was measured with a Malvern® Mastersizer 2000 before and after storage. No increase in droplet size was observed for samples AE1-AE3.

Example 3
Suspended alpha-cypermethrin, cyflumetofen and chlorfenapyr aqueous suspensions AS1-AS4 are water, the respective pesticides, wetting agents, defoamers and, in the case of AS2, surfactants. In the case of C and AS4, it was prepared by mixing the surfactant E. This mixture was wet-milled using a bead mill to a particle size of about 2 μm. For AS2, propylene glycol, biocide, thickener, polymer particles B, and sodium dihydrogen phosphate and disodium hydrogen phosphate were added and mixed to form a uniform suspension. The final concentrations of the ingredients are shown in Table 2.

Table 2: AS1 to AS4, concentrations are given in [wt%].

Example 4
The storage stability of AS1 to AS4 is as follows: one sample at 40°C for 2 weeks, another sample at -10°C to +10°C for 2 weeks, and another sample at -10°C. For 2 weeks each.

Suspension stability was determined by visual observation of the sample. No significant phase separation or hard cake formation occurred for samples AS1 to AS4.

The particle size of the pesticide particles was determined by Malvern Mastersizer 2000 before and after storage. No increase in particle size was observed at all storage temperatures for samples AS1 to AS4.

Example 5
A comparative aqueous emulsion of emulsified pyraclostrobin C-AE3 was prepared in the same manner as sample AE3 of Example 1 (only the use of polymer particles C instead of polymer particles A).

A laboratory rain resistance test was conducted based on the following procedure: Samples were diluted in specific ratios. 1 μL droplet was applied 10 times to the top of corn leaves with a microliter syringe and dried for 1 hour. The corn leaves were mowed and placed in a mesh basket in a recess inside a straight wall glass bottle. The bottle was placed in a rainwater chamber 50 cm below the XR 8006 nozzle. The atomizer was run for about 60 cycles at 0.5 mph until 2 cm of rainwater was collected in the rainwater gauge. The rain wash was partitioned with 10.0 ml of hexane, shaken vigorously and allowed to separate again for several hours. 100 μL of organic phase was collected, transferred to a HPLC vial and evaporated to dryness. The residue was reconstituted with 1.0 ml of acetonitrile, mixed and then subjected to analysis by HPLC-MS/MS. The results are summarized in Table 4. The results showed that the rain resistance of sample AE3 was increased compared to C-AE3.

Table 3: Laboratory rain resistance test results

Example 6
Comparative aqueous suspensions C-AS2 and C-AS4 of suspended cyflumethofen and chlorfenapyr, similar to the samples AS2 and AS4 of Example 1 (only differently using polymer particles C instead of polymer particles A). ) Each was prepared.

The stability of diluted samples AS2 and C-AS2 was evaluated by laboratory experiments. A 2 liter container with a cooling device and paddle stirrer was connected to a pump and a sieve module equipped with a 300 μm sieve and a 150 μm sieve. A 2 liter volume of CIPAC water D was charged to the flask and kept at a temperature of 20°C. A volume of 30 ml of sample AS2 and C-AS2 was added to another flask and the slurry was pumped at 100 l/h for 1 hour. Then 1700 ml of the mixture was pumped out, leaving the remaining volume of 330 ml in the tank. This procedure was repeated 4 times. After the fourth iteration and a recirculation time of 2 hours, the mixture in the instrument was subjected to a rest time of 14-18 hours overnight. The next morning, the mixture was recirculated for 1 hour, followed by a fifth refill and a 5 hour recirculation.

After this final cycle, the sieves were evaluated for coating. If the screen was clogged and/or the flow rate dropped to 0, the test procedure was stopped. The results are summarized in Table 4.

Table 4: Stability of sample AS2 and C-AS2 at dilution

The above results clearly confirm that AS2 showed significantly enhanced stability at dilution compared to C-AS2.

Samples AS4 and C-AS4 were similarly evaluated for stability upon dilution. However, in this test, 200 ml of sample was added to 2 L of CIPAC D water and did not change the slurry throughout the test. The suspension slurry was then pumped through the sieve module (300 μm sieve width and 150 μm sieve width) for 3 hours and left overnight. Then pumping was restarted and the final flow rate was recorded. The results are summarized in Table 5.

Table 5: Stability of diluted samples AS4 and C-AS4.

The above results clearly confirm that AS4 showed significantly enhanced stability at dilution compared to C-AS4.
(Appendix)
(Appendix 1)
An aqueous dispersion comprising a water-insoluble pesticide and polymer particles,
The polymer particles include an alkoxylated copolymerizable surfactant in a polymerized form,
Polymer particles comprise at least 20 wt% of C ₂ -C ₁₂ alkyl (meth) acrylate to a polymeric form relative to the total weight of the monomers,
The aqueous dispersion.
(Appendix 2)
The alkoxylated copolymerizable surfactant has the formula (I):
(In the formula,
R ₁ is a C _{5 to} C ₂₀ hydrocarbon group;
R ₂ and R ₃ are each independently a hydrogen atom or methyl;
AO and AO' are each independently an alkylene oxide group having 2 to 4 carbon atoms;
X is H or SO ₃ ^- ;
The index x ranges from 0 to 12;
The index y is either 0 or 1;
The index z ranges from 1 to 10;
The index m ranges from 1 to 1000;
(The index n is in the range 0 to 1000)
The aqueous dispersion according to Appendix 1, which is a compound according to 1.
(Appendix 3)
The alkoxylated copolymerizable surfactant has the formula (Ia):
(In the formula,
R ⁴ is C ₉ -C ₁₅ alkyl or C ₇ -C ₁₁ alkyl-phenyl,
X is H or SO ₃ ^- ,
(The index o is 3-50)
The aqueous dispersion according to appendix 1 or 2, which is the compound according to item 1.
(Appendix 4)
The aqueous dispersion according to any one of appendices 1 to 3, wherein the polymer particles further comprise in a polymerized form a (meth)acrylamide and a (meth)acrylic acid in a weight ratio of 5:1 to 1:5.
(Appendix 5)
The aqueous dispersion according to any one of appendices 1 to 4, wherein the polymer has a glass transition temperature of 0°C to 20°C.
(Appendix 6)
6. The aqueous dispersion according to any one of appendices 1 to 5, wherein the polymer particles have a particle size of 250 μm or less.
(Appendix 7)
The aqueous dispersion according to any one of appendices 1 to 6, wherein the C _{2 to} C ₁₂ alkyl(meth)acrylate is butyl acrylate.
(Appendix 8)
8. The aqueous dispersion according to any one of appendices 1 to 7, comprising 0.1 to 20% by weight of polymer particles.
(Appendix 9)
9. The aqueous dispersion of claims 1-8, further comprising a non-water miscible solvent containing the pesticide in dissolved form.
(Appendix 10)
The aqueous dispersion according to Appendix 3, wherein R ⁴ is C ₁₀ -C ₁₄ alkyl, X is SO ₃ ^— and the index o is 5-15.
(Appendix 11)
Aqueous dispersion according to any one of appendices 1 to 10, comprising at least 5% by weight of water-insoluble pesticide.
(Appendix 12)
The aqueous dispersion according to any one of appendices 1 to 11, wherein the concentration of the pesticide in the polymer particles is less than 5% by weight based on the total mass of the polymer particles.
(Appendix 13)
A method for preparing an aqueous dispersion as defined in any of supplements 1 to 12, by contacting water, a water-insoluble pesticide, and polymer particles.
(Appendix 14)
A method for controlling phytopathogenic fungi and/or undesired plant growth and/or undesired insect or mite attack, and/or a method for controlling plant growth, which is defined in any one of appendices 1 to 12. Act on each pest, their environment or crops to be protected from each pest, soil and/or undesired plants and/or crops and/or their environment. The method.
(Appendix 15)
A seed comprising the aqueous dispersion as defined in any one of appendices 1 to 12.

Claims (14)

An aqueous dispersion comprising a water-insoluble pesticide and polymer particles,
The polymer particles include an alkoxylated copolymerizable surfactant in a polymerized form,
Polymer particles comprise at least 20 wt% of C ₂ -C ₁₂ alkyl (meth) acrylate to a polymeric form relative to the total weight of the monomers,
The aqueous dispersion. The alkoxylated copolymerizable surfactant has the formula (Ia):
(In the formula,
R ⁴ is C ₉ -C ₁₅ alkyl or C ₇ -C ₁₁ alkyl-phenyl,
X is S O ₃ ^- ,
(The index o is 3-50)
It is a compound according to, aqueous dispersion of claim 1. The aqueous dispersion according to claim 1 or 2 , wherein the polymer particles further comprise (meth)acrylamide and (meth)acrylic acid in a polymerized form in a weight ratio of 5:1 to 1:5. The aqueous dispersion according to any one of claims 1 to 5 , wherein the polymer has a glass transition temperature of 0°C to 20°C. The particle size of the polymer particles is 250μm or less, an aqueous dispersion according to any one of claims 1-4. C ₂ -C ₁₂ alkyl (meth) acrylate is butyl acrylate, an aqueous dispersion according to any one of claims 1-5. Containing 0.1 to 20 wt% of the polymer particles, an aqueous dispersion according to any one of claims 1-6. Water immiscible solvent further comprises an aqueous dispersion according to claim 1-7 comprising a pesticide in dissolved form. The aqueous dispersion according to claim 2 , wherein R ⁴ is C ₁₀ -C ₁₄ alkyl, X is SO ₃ ^- , and the index o is 5-15. At least 5 wt% of water-insoluble pesticide, the aqueous dispersion according to any one of claims 1-9. The concentration of the pesticide in the polymer particles is less than 5% by weight relative to the total weight of the polymer particles, an aqueous dispersion according to any one of claims 1-10. A method for preparing an aqueous dispersion as defined in any of claims 1 to 12 , by contacting water, a water-insoluble pesticide, and polymer particles. A method of modulating method for controlling phytopathogenic fungi and / or growth of undesired plants and / or undesired insect or mite attack and / or plant growth, in any one of claims 1 to 11 Acting the defined aqueous dispersion on each pest, their environment or on the crop to be protected from each pest, on soil and/or on undesired plants and/or crops and/or their environment , Said method. Seeds comprising an aqueous dispersion as defined in any of claims 1 to 11.